Study on the performance of alkali acid modified ZSM-5 catalysts for thiophene alkylation reaction
-
摘要: 以SiO2/Al2O3物质的量比为50的HZSM-5分子筛为原粉,经过一定浓度的NaOH溶液处理后再使用柠檬酸溶液进行酸洗以制备微孔-介孔多级孔HZSM-5催化剂,并研究其在模拟油中的噻吩烷基化反应性能。结果表明,使用柠檬酸溶液进行酸洗可以清除碱处理后孔道内残余的杂质。当柠檬酸溶液浓度为0.5 mol/L时,此时得到的HZ(AC-0.5)催化剂具有适宜的孔径和酸性,因而噻吩烷基化转化率最高,达到95.6%。在HZ(AC-0.5)催化剂上以苯并噻吩作为噻吩衍生物模型化合物,异戊二烯作为烯烃模型化合物,苯作为芳烃模型化合物,分别考察噻吩烷基化反应性能,并分析不同组分的模拟油对噻吩烷基化反应转化率和选择性的影响。结果表明,噻吩烷基化的最佳反应温度是120 ℃,在该温度下苯并噻吩烷基化的转化率高于噻吩烷基化的转化率,当异戊二烯作为烯烃模型化合物后噻吩的转化率会升高,当苯作为芳烃模型化合物后噻吩的转化率会降低。Abstract: HZSM-5 zeolites with SiO2/Al2O3 molar ratio of 50 as the raw material were treated by a certain concentration of NaOH and then impregnated with citric acid solution to prepare microporous and mesoporous hierarchical HZSM-5 catalyst. The catalytic performance of the prepared catalysts for thiophene alkylation reaction was investigated using simulated oil. The results show that the residual impurities in the pores after alkali treatment can be eliminated by acid washing with citric acid solution. When the concentration of the citric acid solution is 0.5 mol/L, the HZ(AC-0.5) catalyst has the appropriate pore size and acidity, so the conversion of thiophene alkylation is the highest, which is up to 95.6%. The performance of thiophene alkylation reaction was also investigated by respectively using dibenzothiophene thiophene derivatives as model compounds, olefin isoprene as model compounds, aromatic benzene as model compound on the HZ (AC-0.5) catalyst. And then we analyzed the influence of different components in the simulated oil on the conversion and selectivity of thiophene alkylation reaction. It has been demonstrated that the optimum reaction temperature of thiophene alkylation reaction is 120℃. At the optimum temperature, the conversion of benothiophene alkylation is higher than that of thiophene alkylation. The conversion of thiophene will be increased when the olefin isoprene is used as model compound. The conversion of thiophene will be decreased when benzene is used as aromatic model compound.
-
Key words:
- alkali treatment /
- acid washing /
- ZSM-5 /
- desulfurization /
- thiophene alkylation
-
表 1 HZSM-5催化剂的相对结晶度和n(SiO2)/n(Al2O3)
Table 1 Relative crystallinity and n(SiO2)/n(Al2O3) of the HZSM-5 catalysts
Sample HZ HZ(A) HZ(AC-0.1) HZ(AC-0.5) HZ(AC-1.0) Relative crystallinity/% 100 78.1 71.6 65.4 59.2 SiO2/Al2O3(molar ratio) 50 33 35 36 39 表 2 HZSM-5催化剂的结构性质变化
Table 2 Pore structural parameters of the HZSM catalysts
Sample ABET/
(m2·g-1)Aext/
(m2·g-1)vmicro/
(mL·g-1)vmeso/
(mL·g-1)daver/
nmHZ 317.9 78.70 11.9 5.4 2.1 HZ(A) 400.6 150.6 9.0 36.4 5.6 HZ(AC-0.1) 412.5 164.7 10.3 37.7 5.7 HZ(AC-0.5) 423.3 173.1 11.1 40.3 5.7 HZ(AC-1.0) 425.4 184.3 10.8 42.8 6.1 表 3 HZSM-5催化剂的噻吩烷基化反应物的转化率
Table 3 Conversion of the thiophene alkylation reaction on the HZAM-5 catalysts
Sample Conversation x/% HZ HZ(A) HZ(AC-0.1) HZ(AC-0.5) HZ(AC-1.0) Thiophene 47.2 82.4 89.3 95.6 70.1 1-hexene 6.3 9.6 15.7 18.1 16.3 Xylene 8.9 11.4 18.3 20.5 15.4 reaction conditions: t=120 ℃, p=1.0 MPa, GHSV=1.0 h-1, t=6 h 表 4 反应温度对原料油各组分的转化率
Table 4 Effect of reaction temperature on convertion of components in the raw oil
Temperature
t/℃Conversion x/% HTS distribution w/% ITS distribution w/% thiophene 1-hexene xylene HT DHT DIT TIT 60 64.8 6.7 13.2 43.2 52.4 93.2 6.8 90 78.2 13.6 15.4 35.4 57.3 89.1 10.9 120 89.6 18.2 20.5 30.3 60.9 87.7 12.3 150 85.4 20.5 28.9 22.6 68.2 75.8 24.2 HTS: thiophene alkyl products; HT: monosubstitutedproducts; DHT; disubstitutedproducts; THT; trisubstitution product;
ITS: olefinicpolymerization; DIT: two polymerization product; TIT: three polymerization product; FIT: four polymerization product; reaction conditions: p=1.0 MPa, GHSV=1.0 h-1, t=6 h表 5 噻吩烷基化反应物转化率及产物分布
Table 5 Conversion and product distribution of the thiophene alkylation reaction on the catalyst
Model oil Conversion x/% HTS distribution w/% HXS distribution w/% thiophene and its derivatives 1-hexene xylene HT DHT THT HX DHX 1# 95.6 18.1 20.5 30.3 60.9 8.8 89.2 10.8 2# 98.6 14.6 16.9 59.8 37.2 3.0 74.6 25.4 3# 90.3 11.5 12.9 47.4 49.5 3.1 64.8 35.2 4# 86.5 9.6 7.5 42.1 56.1 1.6 50.3 49.7 HTS: thiophene alkyl products; HT: mo nosubstituted products; DHT; disubstituted products; THT; trisubstitution product;
HXS: aromatic alkyl products; HX: single substitution products; DHX: two substitution products; FHT: four substitution products; reaction conditions: t=120 ℃, p=1.0 MPa, GHSV=1.0 h-1, t=6 h表 6 噻吩烷基化反应物转化率及产物分布
Table 6 Conversion and product distribution of the thiophene alkylation reaction on the catalysts
Modeloil Conversion x/% HTS distribution w/% ITS distribution w/% thiophene olefin xylene HT DHT THT FHT DIT TIT FIT 1# 95.6 18.1 20.5 30.3 60.9 8.8 0 87.7 12.3 0 5# 96.6 25.4 26.1 47.5 27.2 20.5 4.8 74.3 23.8 1.9 6# 97.2 28.9 28.9 50.6 21.7 22.3 5.4 70.1 27.5 2.4 7# 98.3 33.4 32.4 57.4 16.3 29.4 6.9 64.9 30.8 4.3 reaction conditions: t=120℃, p=1.0 MPa, GHSV=1.0 h-1, t=6 h 表 7 噻吩烷基化反应物转化率及产物分布
Table 7 Conversion and product distribution of the thiophene alkylation reaction on the
Model oil Conversion x/% HTS distribution w/% HXS distribution w/% thiophene 1-hexene aromatics HT DHT THT HX DHX 1# 95.6 18.1 20.5 30.3 60.9 8.8 89.2 10.8 8# 90.3 27.4 25.7 21.7 75.7 2.6 50.3 49.7 reaction condition: t=120 ℃, p=1.0 MPa, GHSV=1.0 h-1, t=6 h -
[1] 刘继华, 赵乐平, 方向晨, 宋永一. FCC汽油选择性加氢脱硫技术开发及工业应用[J].炼油技术与工程, 2007, 37(7): 4-7. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=lysz200707003&dbname=CJFD&dbcode=CJFQLIU Ji-hua, ZHAO Le-ping, FANG Xiang-chen, SONG Yong-yi. Development and commercial application of selective hydrodesulfurization technology for FCC gasoline[J]. Petro Ref Eng, 2007, 37(7): 4-7. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=lysz200707003&dbname=CJFD&dbcode=CJFQ [2] 马健, 刘冬梅, 王海彦, 赵伟林.烷基化脱除FCC汽油中噻吩硫研究进展[J].当代化工, 2013, (9): 1288-1290. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=syhh201309037&dbname=CJFD&dbcode=CJFQMA Jian, LIU Dong-mei, WANG Hai-yan, ZHAO Wei-lin. Progress in alkylation removal of thiophene sulfur from FCC gasoline[J]. Modern Chem Ind, 2013, (9): 1288-1290. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=syhh201309037&dbname=CJFD&dbcode=CJFQ [3] GISLASONL J. Phillips sulfur-removal processne nears commercialization[J]. Oil Gas J, 2001, 99(47): 72-76. http://www.cheric.org/research/tech/periodicals/view.php?seq=5364 [4] 罗国华, 徐新, 佟泽民.分子筛催化噻吩类硫化物与烯烃烷基化脱硫研究[J], 化学反应工程与工艺, 2005, 21(2): 133-137. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=hxfy200502008&dbname=CJFD&dbcode=CJFQLUO Guo-hua, XU Xin, TONG Ze-min. Study on alkylation desulfurization of thiophene and olefin by molecular sieve catalyst[J]. Chem React Eng Technol, 2005, 21(2): 133-137. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=hxfy200502008&dbname=CJFD&dbcode=CJFQ [5] 赵岑, 刘冬梅, 魏民, 孙志岩, 王海岩.多级孔ZSM-5分子筛的制备及催化噻吩烷基化性能研究[J].燃料化学学报, 2013, 41(10): 1256-1261. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract18282.shtmlZHAO Cen, LIU Dong-mei, WEI Min, SUN Zhi-yan, WANG Hai-yan. Preparation and catalytic performance of ZSM-5 molecular sieve with hierarchical pore[J]. J Fuel Chem Technol, 2013, 41(10): 1256-1261. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract18282.shtml [6] 史荣会, 潘蓉, 吴利红, 张冉冉.固体酸催化剂烷基化脱噻吩硫的研究进展[J].现代化工, 2014, 34(9): 32-35. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=xdhg201409010&dbname=CJFD&dbcode=CJFQSHI Rong-hui, PAN Rong, WU Li-hong, ZHANG Ran-ran. Progress in alkylation of thiophene with sulfur by solid acid catalyst[J]. Modern Chem Ind, 2014, 34(9): 32-35. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=xdhg201409010&dbname=CJFD&dbcode=CJFQ [7] 罗国华, 徐新, 杨春育, 佟泽民, 彭少逸.大孔磺酸树脂固载AlCl3用于噻吩与烯烃的烷基化反应[J].过程工程学报, 2003, 3(1): 18-23. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=hgyj200301003&dbname=CJFD&dbcode=CJFQLUO Guo-hua, XU Xin, YANG Chun-yu, TONG Ze-min, PENG Shao-yi. Study on alkylation of thiophene with olefins by macroporous resin supported AlCl3[J]. Chin J Process Eng, 2003, 3(1): 18-23. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=hgyj200301003&dbname=CJFD&dbcode=CJFQ [8] 姜蕾, 张占柱, 毛俊义, 渠红亮, 吴梅.采用改性磺酸树脂催化剂的催化裂化汽油的烷基化脱硫[J].石油学报(石油加工), 2006, 22(1): 22-26. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=sxjg200601003&dbname=CJFD&dbcode=CJFQJIANG Lei, ZHANG Zhan-zhu, MAO Jun-yi, QU Hong-liang, WU Mei. Alkylation Desulfurization of FCC gasoline with modified sulfonic acid resin catalyst[J]. Acta Pet Sin(Pet Process Sect), 2006, 22(1): 22-26. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=sxjg200601003&dbname=CJFD&dbcode=CJFQ [9] OGURA M, SHINOMIYA S Y, TATENO J, NARA Y, NOMURA M, KIKUCHI E, MATSUKATA M. Alkali-treatment technique—new method for modification of structural and acid-catalytic properties of ZSM-5 zeolites[J]. Appl Catal A: Gen, 2001, 219(1/2): 33-43. http://www.sciencedirect.com/science/article/pii/S0926860X01006457 [10] 宋禹奠. 大介孔孔径的多级孔ZSM-5沸石的碳质软模板法制备、改性与催化性能研究[D]. 北京: 中国科学院大学, 2013. http://d.wanfangdata.com.cn/Thesis/Y2333180SONG Yu-ji. Study on preparation, modification and catalytic properties of ZSM-5 mesoporous zeolite with large mesoporous pores by carbon soft template method[D]. Beijing: University of Chinese Academy of Sciences, 2013. http://d.wanfangdata.com.cn/Thesis/Y2333180 [11] 刁振恒. 多级孔HZSM-5分子筛的合成及其超临界烃催化裂解性能[D]. 天津: 天津大学, 2015. http://cdmd.cnki.com.cn/Article/CDMD-10056-1016117378.htmDIAO Zhen heng. Synthesis of multi hole HZSM-5 zeolite and its catalytic performance for supercritical catalytic cracking[D]. Tianjin: Tianjin University, 2015. http://cdmd.cnki.com.cn/Article/CDMD-10056-1016117378.htm [12] 陆璐, 张会贞, 朱学栋.多级孔ZSM-5分子筛的合成及催化苯、甲醇烷基化反应的研究[J].石油学报(石油加工), 2012, 28(s1): 111-115. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=sxjg2012s1030&dbname=CJFD&dbcode=CJFQLU Lu, ZHANG Hui-zhen, ZHU Xue-dong. Synthesis of multi hole ZSM-5 zeolite and alkylation of benzene and methanol[J]. Acta Pet Sin(Pet Process Sect), 2012, 28(s1): 111-115. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=sxjg2012s1030&dbname=CJFD&dbcode=CJFQ [13] 马健, 刘冬梅, 魏民, 王海彦, 王坤, 张晶卫. Na2CO3溶液处理对Ni-Mo/HZSM-5分子筛硫醚化催化性能的影响[J].燃料化学学报, 2014, 42(9): 1128-1134. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract18493.shtmlMA Jian, LIU Dong-mei, WEI Min, WANG Hai-yan, WANG Kun, ZHANG Jing-wei. Effect of Na2CO3 solution treatment on properties of Ni-Mo/HZSM-5 thioetherfication catalyst[J]. J Fuel Chem Technol, 2014, 42(9): 1128-1134. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract18493.shtml [14] TAGO T, KONNO H, SAKAMOTO M, NAKASAKA M, MASUDA T. Selective synthesis for light olefins from acetone over ZSM-5 zeolites with nano-and macro-crystal sizes[J]. Appl Catal A: Gen, 2011, 403(1/2): 183-191. http://www.sciencedirect.com/science/article/pii/S0926860X11003917 [15] 宋春敏, 姜杰, 乔柯, 孟祥滨, 阎子峰.微孔-介孔复合结构分子筛的合成及表征研究[J].分子催化, 2006, 20(4): 294-299. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=fzch200604001&dbname=CJFD&dbcode=CJFQSONG Chun-min, JIANG Jie, QIAO Ke, MENG Xiang-bin, YAN Zi-feng. Synthesis and characterization of microporous mesoporous composite molecular sieves[J]. Mol Catal, 2006, 20(4): 294-299. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=fzch200604001&dbname=CJFD&dbcode=CJFQ [16] Song Y Q, Feng Y L, Liu F, KANG C L, ZHOU X L, XU Y L, YU G X. Effect of variations in pore structure and acidity of alkali treated ZSM-5 on the isomerization performance[J]. J Mol Catal A: Chem, 2009, 10(1/2): 130-137. http://www.sciencedirect.com/science/article/pii/S1381116909002817 [17] 田震, 秦张峰, 董梅, 王建国.柠檬酸改性对Hβ分子筛烷基化性能的影响[J].石油化工, 2004, 33(s1): 175-176. http://d.wanfangdata.com.cn/conference_5910051.aspxTIAN Zhen, QIN Zhang-feng, DONG Mei, WANG Jian-guo. Effect of citric acid modification on the alkylation of Hβ zeolite[J]. Petro Chem Ind, 2004, 33(S1): 175-176. http://d.wanfangdata.com.cn/conference_5910051.aspx [18] LI S, LI Y P, DI C Y, ZHANG P F, RAN R L. Modification and catalyst performance of ZSM-5 zeolite by treatment with TPAOH/NaOH mixed alkali[J]. J Fuel Chem Technol, 2012, 40(2): 583-588. http://en.cnki.com.cn/Article_en/CJFDTOTAL-RLHX201205012.htm [19] GROEN J C, PEFFER L A A, MOULIJN J A, PÉREZ-RAMÍREZ. Mesoporosity development in ZSM-5 zeolite upon optimized desilination conditions in alkaline medium[J]. Colloid Surf A, 2004, 241(1/3): 53-58. http://www.sciencedirect.com/science/article/pii/S0927775704002067 [21] CAICEDO-REALPE R, PÉRÉZ-RAMÍREZ J. Mesoporous ZSM-5 zeolites prepared by a two-step route comprising sodium aluminate and acid treatments[J]. Microporous Mesoporous Mater, 2010, 128(1/3): 91-100. http://www.sciencedirect.com/science/article/pii/S1387181109003758 [22] 朱杰, 钱广, 张薇薇, 苏雅茹, 罗雨妍, 李璐, 朱龙凤.介孔Beta沸石的后处理法制备及其在合成2-乙基蒽醌中的催化性能[J].浙江化工, 2016, 47(7): 27-30. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=zjhg201607008&dbname=CJFD&dbcode=CJFQZHU Jie, QIANG Guang, ZHANG Wei-wei, SU Ya-ru, LUO Yu-yan, LI Lu, ZHU Long-feng. Preparation of mesoporous Beta zeolite and its catalytic performance in the synthesis of 2-ethyl anthraquinone[J]. Zhejiang Chem Eng, 2016, 47(7): 27-30. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=zjhg201607008&dbname=CJFD&dbcode=CJFQ [23] 贾丹丹, 苏明瑾, 张兴刚, 宋林花, 姜翠玉.酸处理改性Hβ分子筛催化合成乙基蒽醌[J].工业催化, 2014, 22(6): 466-472. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=gych201406015&dbname=CJFD&dbcode=CJFQJIA Dan-dan, QIN Ming-jin, ZHANG Xing-gang, SONG Lin-hua, JIANG Cui-yu. Catalytic synthesis of Ethyl Anthraquinone catalyzed by Hβ modified zeolite by acid treatment[J]. Ind Catal, 2014, 22(6): 466-472. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=gych201406015&dbname=CJFD&dbcode=CJFQ [24] 刘冬梅, 翟玉春, 马健, 王海彦.不同碱处理制备多级孔HZSM-5催化剂及噻吩烷基化性能研究[J].燃料化学学报, 2015, 43(4): 462-469. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract18611.shtmlLIU Dong-mei, ZHAI Yu-chun, MA Jian, WANG HAi-yan. Preparation of multi hole HZSM-5 catalysts and thiophene alkylation properties by different alkali treatment[J]. J Fuel Chem Technol, 2015, 43(4): 462-469. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract18611.shtml [25] 金文清, 赵国良, 滕加伟, 谢在库氢氧化钠改性ZSM-5分子筛的碳四烯烃催化裂解性能[J].化学反应工程与工艺, 2007, 23(3): 193-199. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=hxfy200703002&dbname=CJFD&dbcode=CJFQJIN Wen-qing, ZHAO Guo-liang, TENG Jia-wei, XIE Zai-ku. Catalytic cracking performance of carbon four olefin modified by sodium hydroxide[J]. Chem React Eng Process, 2007, 23(3): 193-199. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=hxfy200703002&dbname=CJFD&dbcode=CJFQ [26] 肖何, 高俊华, 胡津仙, 章斌, 刘平, 张侃.酸碱改性HZSM-5分子筛上甲醇制取均四甲苯的研究[J].燃料化学学报, 2013, 41(1): 102-109. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract18108.shtmlXIAO He, GAO Jun-hua, HU Jin-xian, ZHANG Bin, LIU Ping, ZHANG Kan. Study on the synthesis of four toluene from methanol on acid modified HZSM-5 zeolite[J]. J Fuel Chem Technol, 2013, 41(1): 102-109. http://manu60.magtech.com.cn/rlhxxb/CN/abstract/abstract18108.shtml [27] 潘兴朋, 吴相英, 杜君, 钱明超, 余江. 碱处理Beta分子筛吸附脱硫动力学[J]. 化工学报, 2016, (9): 3748-3754. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=hgsz201609028&dbname=CJFD&dbcode=CJFQPAN Xing-peng, Xiang-ying, DU Jun, QIAN Ming-chao, YU Jiang. Kinetics of adsorption desulfurization of Beta zeolite by alkali treatment[J]. J Chem Ind, 2016, (9): 3748-3754. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=hgsz201609028&dbname=CJFD&dbcode=CJFQ [28] 孔飞飞, 王海彦, 项洪涛, 刘冬梅. ZSM-5催化剂加氢脱硫及烯烃芳构化反应研究[J].石油炼制与化工, 2016, 47(3): 60-66. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=sylh201603017&dbname=CJFD&dbcode=CJFQKONG Fei-fei, WANG Hai-yan, XIANG Hong-tao, LIU Dong-mei. Study on hydrodesulfurization of ZSM-5 catalyst and aromatization of olefins[J]. Petro Ref Chem Ind, 2016, 47(3): 60-66. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=sylh201603017&dbname=CJFD&dbcode=CJFQ [29] 聂宁, 沈健. USY分子筛催化噻吩烷基化性能的研究[J].石化技术与应用, 2013, 31(2): 110-114. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=izhm201302006&dbname=CJFD&dbcode=CJFQNIE Ning, SHEN Jian. Study on catalytic alkylation of thiophene with USY zeolite[J]. Petro Technol Appl, 2013, 31(2): 110-114. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=izhm201302006&dbname=CJFD&dbcode=CJFQ [30] 张泽凯, 蒋晖, 刘盛林, 王清遐, 徐龙伢.汽油烷基化脱硫反应中噻吩及其衍生物的烷基化性能[J].催化学报, 2006, 27(4): 309-313. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=chua200604006&dbname=CJFD&dbcode=CJFQZHANG Ze-kai, JIANG Hui, LIU Sheng-lin, WANG Qing-xia, XU Long-ya. Alkylation of thiophene and its derivatives in gasoline alkylation desulfurization[J]. Catalysis, 2006, 27(4): 309-313. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=chua200604006&dbname=CJFD&dbcode=CJFQ [31] 张泽凯, 刘盛林, 杜喜研, 曾蓬, 王清遐, 徐龙伢.芳烃烷基化反应性能对烷基化脱除汽油中硫化物过程的影响[J].石油化工, 2006, 35(2): 113-117. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=syhg200602001&dbname=CJFD&dbcode=CJFQZHANG Ze-kai, LIU Sheng-lin, DU Xi-yan, ZENG Peng, WANG Qing-xia, XU Long-ya. Effects of aromatics alkylation on the removal of sulfides in gasoline by alkylation[J]. Petro Chem, 2006, 35(2): 113-117. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=syhg200602001&dbname=CJFD&dbcode=CJFQ [32] 张泽凯, 牛雄雷, 朱向学, 刘盛林, 王清遐, 徐龙伢.汽油烷基化脱硫中己烯的聚合及对噻吩烷基化的影响[J].中国石油大学学报, 2008, 32(1): 123-127. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=sydx200801031&dbname=CJFD&dbcode=CJFQZHANG Ze-kai, NIU Xiong-lei, ZHU Xiang-xue, LIU Sheng-lin, WANG Qing-xia, XU Long-ya. The polymerization of ethylene and its influence on alkylation in the process of gasoline alkylation desulfurization[J]. J China Univ Pet, 2008, 32(1): 123-127. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=sydx200801031&dbname=CJFD&dbcode=CJFQ